A chiral quaternary ammonium amide was generated in situ from N,O-bis(trimethylsilyl)-A C H T U N G T R E N N U N G acetamide (BSA) as non-nucleophilic Brønsted base precursor and the combination of chiral quaternary ammonium halide/sodium aryloxide as chiral Lewis base. This system was applied to an anti-selective organocatalytic direct vinylogous aldol (ODVA) reaction of (5H)-furan-2-one derivatives with aldehydes. Several 5-(1'-hydroxy)-g-butenolides were obtained in good diastereomeric ratios (up to 95/5) and excellent enantioselectivities (up to 94%) with both aliphatic or (hetero)aromatic aldehydes, so providing a rare example of general and efficient conditions for the ODVA reaction.